Kinetics and Mechanism of Transformations of Aliphatic Alcohol Molecules Under Multiphoton IR Excitation

The main channels for transformations of C 2 H 5 OH, iso-CH 3 H 7 OH and n-C 3 H 7 OH molecules under IR multiphoton excitation are the monomolecular reactions of dehydration (1), andC α − C β bond breaks (2). The ratio of the yields of reactions (1) and (2), γ, is determined by the molecules' structure, radiation energy density, the pressure of alcohol vapors and inert gas. The direction of the alcohol molecules' transformations under IR MPE, under thermal equilibrium conditions, differs from pyrolysis, when the chain processes of C 2 H 5 OH and C 3 H 7 OH molecules dehydrogenation, and CH 4 splitting-out from n-C 3 H 7 OH molecules are developing. Reactions of H and CH 3 radicals with alcohol molecules under laser initiation do not lead to the development of chains due to the high rate of H atoms diffusion from reaction zone and effectiverecombination of CH 3 radicals.